US4937383A - Process for manufacturing amines from olefins - Google Patents

Process for manufacturing amines from olefins Download PDF

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US4937383A
US4937383A US07/246,985 US24698588A US4937383A US 4937383 A US4937383 A US 4937383A US 24698588 A US24698588 A US 24698588A US 4937383 A US4937383 A US 4937383A
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olefin
ammonium
mole
tert
isobutene
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US07/246,985
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Yves Brigandat
Jacques Kervennal
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Arkema France SA
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Atochem SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
    • C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes

Definitions

  • the invention pertains to a process for manufacturing amines by reacting at a high temperature a monoolefin with ammonia or a primary or secondary amine in the presence of a catalyst.
  • the first process consists of working at a temperature ranging between 100° C. and 250° C. in the presence of a catalyst with a base of ruthenium or iron dissolved in a solvent medium. It seems to be suitable only for ethylene and has the disadvantage of not selectively producing a specific amine.
  • the second process consists of working at a temperature ranging preferably between 250° C. and 350° C. in the presence of an ammonium halide as a catalyst.
  • the latter is preferably accompanied by a transition metal-based promotor with no catalytic activity of its own, which may be either a transition metal halide or an ammonium salt of a transition metal oxyacid.
  • an ammonium halide is also suitable for obtaining amines from olefins by liquid-phase photocatalysis.
  • ammonium halides are specifically distinguished in the prior art among the compounds containing a NH 4 ammonium group.
  • the present invention has in fact as its object a process for the manufacturing of an amine by reacting at a high temperature a monoolefin or the alcohol corresponding to its hydration or of a mixture of a monoolefin and the said alcohol with ammonia or a primary or secondary amine in the presence of a catalyst and a solvent, characterized by the fact that the catalyst is ammonium sulfate (NH 4 ) 2 SO 4 or a double sulfate of ammonium and a transition metal.
  • a catalyst is ammonium sulfate (NH 4 ) 2 SO 4 or a double sulfate of ammonium and a transition metal.
  • Ammonium sulfate can be used as is, for example, it can be formed from ammonia and sulfuric acid or ammonium acid sulfate.
  • Double sulfates of ammonium and transition metal that are suitable for the invention are, for example, those of the alum type of the general formula XNH 4 (SO 4 ) 2 .12H 2 O, in which X represents the transition metal.
  • the transition metal is selected from among chromium, rhodium, vanadium and iron, with the iron usually being preferred to the others.
  • the catalyst is used in an amount that is generally such that the catalyst/olefin molar ratio ranges between ca. 0.01 and 0.5.
  • the NH3 (or primary or secondary amine)/olefin molar ratio usually ranges between 1/1 and 10/1 and is preferably at least equal to 2/1.
  • the temperature at which the process according to the invention is conducted is at an elevated temperature, generally ranges between ca. 200° C. and 450° C. to ensure sufficiently high conversion of the olefin and selectivity of amine produced.
  • the temperature will generally be not greater than ca. 300° C.
  • the pressure is the autogenous pressure provided by the reaction medium under the conditions selected for execution of the process.
  • isobutene for example, it is practically no less than ca. 100 bars absolute.
  • the olefin and amine which, besides NH 3 , is called on to react with it are selected among those commonly cited in connected with a process of the type specific to the invention, for example, in European patent application No. EP-0,200,923.
  • those with two to four carbon atoms in their molecule such as isobutene, are preferred.
  • Ammonia is often selected in preference to an amine for reasons of cost and availability, and for reasons of selectivity and importance of primary amines.
  • the solvents used can be of the type of those cited in European patent application No. EP-0,200,923, but water, the alcohol corresponding to the hydration of the olefin, or their mixtures are preferred.
  • the olefin, alcohol, ammonia or amine recoverable in terms of the procedures according to the invention may obviously be profitably recycled.
  • the length of the procedure according to the invention depends on the selection of the olefin and reaction parameters. It often ranges between ca. a few dozen minutes and about 15 hours, generally between one and ten hours.
  • the conversion of olefin to amine is expressed in number of moles of olefin converted to amine per 100 moles of olefin used.
  • the amine selectivity is expressed by the ratio of number of olefin moles converted to amine to total of olefin moles converted per 100 moles of olefin used.
  • alcohol When alcohol intervenes, it is blended with the olefin for the determination of conversion and selectivity, with the alcohol and olefin being recyclable.
  • a mixture formed from 90 g (5.3 moles) of anhydrous ammonia, 56 g (1 mole) of isobutene, 20 g (0.15 mole) of ammonium sulfate (NH 4 ) 2 SO 4 and 360 g (20 moles) of water is kept at 250° C. for ten hours while agitating in a one-liter stainless-steel autoclave.
  • the pressure is the autogenous pressure.
  • a mixture containing the same quantities of isobutene, ammonia and water as in Example 1 and 6.6 g (0.05 mole) of ammonium sulfate are kept at 240° C. for eight hours while agitating under autogenous pressure in the autoclave described in Example 1.
  • Example 2 is repeated, with the difference that the ammonium sulfate amount used is equal to 26.4 g (0.2 mole) and that the mixture is kept at 240° C. for only five hours.
  • a mixture formed from 74 g (1 mole) of tert-butanol, 90 g (5.3 moles) of anhydrous ammonia, 40 g (0.3 mole) of ammonium sulfate and 360 g (20 moles) of water is kept while agitating at 240° C. for ten hours under autogenous pressure in the autoclave described in Example 1.
  • Example 1 is repeated using 28 g (0.5 mole) of isobutene and 37 g (0.5 mole) of tert-butanol.
  • Example 5 By way of comparison, the repeating of Example 5 using NH 4 Cl instead of (NH 4 ) 2 SO 4 , in equal molar amount, yields the formation of only 20 g (0.27 mole) of tert-butylamine.
  • a mixture formed from 74 g (1 mole) of tert-butanol, 90 g (5.3 moles) of anhydrous ammonia and 9 g (0.07 mole) of ammonium sulfate is kept under agitation for five hours at 240° C. in the autoclave described in Example 1.
  • Example 1 is repeated, with the following differences: The double sulfate of ammonium and iron, NH 4 Fe(SO 4 ) 2 , is used at the rate of 11.3 g (0.05 mole) instead of plain ammonium sulfate, and the residence time at the temperature of 250° C. is five hours instead of ten hours.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A process for the manufacture of amines by reacting at an elevated temperature an olefin selected from a monoolefin, the alcohol corresponding to its hydration, or a mixture of the monoolefin and the alcohol with ammonia or a primary or secondary amine in the presence of a catalyst and a solvent, said catalyst being ammonium sulfate of a double sulfate of ammonium and a transition metal.

Description

BACKGROUND OF THE INVENTION
The invention pertains to a process for manufacturing amines by reacting at a high temperature a monoolefin with ammonia or a primary or secondary amine in the presence of a catalyst.
It is known how to perform such a reaction, for example, using the processes described in European patent application Nos. EP-0,039,061 and EP-0,200,923. The first process consists of working at a temperature ranging between 100° C. and 250° C. in the presence of a catalyst with a base of ruthenium or iron dissolved in a solvent medium. It seems to be suitable only for ethylene and has the disadvantage of not selectively producing a specific amine. The second process consists of working at a temperature ranging preferably between 250° C. and 350° C. in the presence of an ammonium halide as a catalyst. The latter is preferably accompanied by a transition metal-based promotor with no catalytic activity of its own, which may be either a transition metal halide or an ammonium salt of a transition metal oxyacid.
According to U.S. Pat. Nos. 4,459,191 and 4,483,747 an ammonium halide is also suitable for obtaining amines from olefins by liquid-phase photocatalysis.
Thus, the ammonium halides are specifically distinguished in the prior art among the compounds containing a NH4 ammonium group.
SUMMARY OF THE INVENTION
It has now been found that compounds with NH4 groups other than halides are particularly suited to obtaining an amine effectively and selectively from a monoolefin, as well as from the alcohol corresponding to hydration of the olefin or mixtures of an olefin and said alcohol.
The present invention has in fact as its object a process for the manufacturing of an amine by reacting at a high temperature a monoolefin or the alcohol corresponding to its hydration or of a mixture of a monoolefin and the said alcohol with ammonia or a primary or secondary amine in the presence of a catalyst and a solvent, characterized by the fact that the catalyst is ammonium sulfate (NH4)2 SO4 or a double sulfate of ammonium and a transition metal.
DETAILED DESCRIPTION
Ammonium sulfate can be used as is, for example, it can be formed from ammonia and sulfuric acid or ammonium acid sulfate.
Double sulfates of ammonium and transition metal that are suitable for the invention are, for example, those of the alum type of the general formula XNH4 (SO4)2.12H2 O, in which X represents the transition metal.
Most generally, the transition metal is selected from among chromium, rhodium, vanadium and iron, with the iron usually being preferred to the others.
The catalyst is used in an amount that is generally such that the catalyst/olefin molar ratio ranges between ca. 0.01 and 0.5.
The NH3 (or primary or secondary amine)/olefin molar ratio usually ranges between 1/1 and 10/1 and is preferably at least equal to 2/1.
The temperature at which the process according to the invention is conducted is at an elevated temperature, generally ranges between ca. 200° C. and 450° C. to ensure sufficiently high conversion of the olefin and selectivity of amine produced.
For an olefin containing four carbon atoms in its molecule, as for example isobutene, the temperature will generally be not greater than ca. 300° C.
The pressure is the autogenous pressure provided by the reaction medium under the conditions selected for execution of the process. In the case of isobutene, for example, it is practically no less than ca. 100 bars absolute.
The olefin and amine which, besides NH3, is called on to react with it are selected among those commonly cited in connected with a process of the type specific to the invention, for example, in European patent application No. EP-0,200,923. Among the monoolefins to which the invention thus applies and which have two to eight carbon atoms in their molecule, those with two to four carbon atoms in their molecule such as isobutene, are preferred.
That which is stated above for the olefin is true for the alcohol corresponding to its hydration as well as for the olefin and the said alcohol in a mixture, for example, for isobutene, tert-butanol or their mixtures.
Ammonia is often selected in preference to an amine for reasons of cost and availability, and for reasons of selectivity and importance of primary amines.
The solvents used can be of the type of those cited in European patent application No. EP-0,200,923, but water, the alcohol corresponding to the hydration of the olefin, or their mixtures are preferred.
The olefin, alcohol, ammonia or amine recoverable in terms of the procedures according to the invention may obviously be profitably recycled.
The length of the procedure according to the invention depends on the selection of the olefin and reaction parameters. It often ranges between ca. a few dozen minutes and about 15 hours, generally between one and ten hours.
The invention will be further described in connection with the following examples which are set forth for purposes of illustration only.
They pertain to isobutene and the amine formed is tert-butylamine ##STR1## whose value in industry is progressively increasing, particularly in the plant health field.
The conversion of olefin to amine is expressed in number of moles of olefin converted to amine per 100 moles of olefin used.
The amine selectivity is expressed by the ratio of number of olefin moles converted to amine to total of olefin moles converted per 100 moles of olefin used.
When alcohol intervenes, it is blended with the olefin for the determination of conversion and selectivity, with the alcohol and olefin being recyclable.
It has been confirmed that no amine forms in the absence of a catalyst.
EXAMPLE 1
A mixture formed from 90 g (5.3 moles) of anhydrous ammonia, 56 g (1 mole) of isobutene, 20 g (0.15 mole) of ammonium sulfate (NH4)2 SO4 and 360 g (20 moles) of water is kept at 250° C. for ten hours while agitating in a one-liter stainless-steel autoclave. The pressure is the autogenous pressure.
25.6 (0.35 mole) of tert-butylamine are obtained, corresponding to a 35% conversion of isobutene to amine, in addition to untransformed isobutene and 14.8 g (0.2 mole) of tert-butanol.
EXAMPLE 2
A mixture containing the same quantities of isobutene, ammonia and water as in Example 1 and 6.6 g (0.05 mole) of ammonium sulfate are kept at 240° C. for eight hours while agitating under autogenous pressure in the autoclave described in Example 1.
11 g (0.15 mole) of tert-butylamine are obtained, corresponding to a 15% conversion of isobutene to amine, in addition to untransformed isobutene and 16.3 g (0.22 mole) of tert-butanol.
EXAMPLE 3
Example 2 is repeated, with the difference that the ammonium sulfate amount used is equal to 26.4 g (0.2 mole) and that the mixture is kept at 240° C. for only five hours.
16.8 g (0.23) of tert-butylamine are obtained, corresponding to a 23% isobutene conversion rate, in addition to untransformed isobutene and 14.8 g (0.2 mole) of tert-butanol.
EXAMPLE 4
A mixture formed from 74 g (1 mole) of tert-butanol, 90 g (5.3 moles) of anhydrous ammonia, 40 g (0.3 mole) of ammonium sulfate and 360 g (20 moles) of water is kept while agitating at 240° C. for ten hours under autogenous pressure in the autoclave described in Example 1.
In this manner, 22 g (0.3 mole) of tert-butylamine are obtained; a 30% conversion of tert-butanol to amine, in addition to 32 g (0.57 mole) of isobutene.
EXAMPLE 5
Example 1 is repeated using 28 g (0.5 mole) of isobutene and 37 g (0.5 mole) of tert-butanol.
33.6 g (0.46 mole) of tert-butylamine are obtained; a 46% cumulative conversion of olefin and tert-butanol, in addition to 21.3 g (0.38 mole) of isobutene, while 11.8 g (0.16 mole) of tert-butanol remain.
By way of comparison, the repeating of Example 5 using NH4 Cl instead of (NH4)2 SO4, in equal molar amount, yields the formation of only 20 g (0.27 mole) of tert-butylamine.
EXAMPLE 6
A mixture formed from 74 g (1 mole) of tert-butanol, 90 g (5.3 moles) of anhydrous ammonia and 9 g (0.07 mole) of ammonium sulfate is kept under agitation for five hours at 240° C. in the autoclave described in Example 1.
7.3.g (0.1 mole) of tert-butylamine and 44.4 g of isobutene form.
EXAMPLE 7
Example 1 is repeated, with the following differences: The double sulfate of ammonium and iron, NH4 Fe(SO4)2, is used at the rate of 11.3 g (0.05 mole) instead of plain ammonium sulfate, and the residence time at the temperature of 250° C. is five hours instead of ten hours.
14.5 g (0.2 mole) of tert-butylamine are obtained, corresponding to a 20% conversion of olefin to amine, in addition to untransformed isobutene and 15 g (0.2 mole) of tert-butanol.
In all the above examples according to the invention, the formation of oily products was not observed, and the selectivity of the tert-butylamine reaction was always practically equal to 100% or very close to 100% to within the nearest measurement errors.
While the invention has been described in connection with a preferred embodiment, it is not intended to limit the scope of the invention to the particular form set forth, but, on the contrary, it is intended to cover such alternatives, modifications and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims.

Claims (10)

What is claimed is:
1. A process for the manufacture of amines by reacting at an elevated temperature an olefin selected from a monoolefin, the alcohol corresponding to its hydration, or a mixture of said monoolefin and the said alcohol with ammonia or a primary or secondary amine in the presence of a catalyst and a solvent, said catalyst being ammonium sulfate or a double sulfate of ammonium and a transition metal.
2. The process of claim 1, wherein the transition metal is selected from chromium, rhodium, vanadium or iron.
3. The process of claim 2, wherein the double sulfate of ammonium and a transition metal is of the alum type.
4. The process of claim 3 wherein the ##EQU1## molar ratio ranges between 0.01 and 0.5.
5. The process of claim 4, wherein the ##EQU2## molar ratio ranges between one and ten.
6. The process of claim 5, where the ##EQU3## molar ratio is at least equal to 2.
7. The process according to any of claims 1 to 6, wherein the reaction of the olefin with ammonia or primary or secondary amine is performed at a temperature ranging between about 200° C. to 450° C. under autogenous pressure.
8. The process according to any of claims 1 to 6, wherein the solvent is water, or the alcohol corresponding to that obtained when the olefin is hydrated, or mixtures thereof.
9. The process of any one of any of claims 1 to 6 wherein the olefin has 2 to 8 carbon atoms, the reaction is carried out at a temperature of about 200° C. to 450° C. under autogenous pressure, and the solvent is water, or the alcohol corresponding to that obtained when the olefin is hydrated, or mixtures thereof.
10. The process of any one of claims 1 to 6 wherein the olefin is selected from isobutene, tert-butanol, or mixtures thereof.
US07/246,985 1987-10-02 1988-09-20 Process for manufacturing amines from olefins Expired - Fee Related US4937383A (en)

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FR8713873 1987-10-02
FR8713873A FR2621313B1 (en) 1987-10-02 1987-10-02 PROCESS FOR THE MANUFACTURE OF AMINES FROM OLEFINS

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EP (1) EP0310527B1 (en)
AT (1) ATE72561T1 (en)
DE (2) DE3868376D1 (en)
ES (1) ES2008066T3 (en)
FR (1) FR2621313B1 (en)
GR (2) GR890300088T1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108610260A (en) * 2018-06-08 2018-10-02 浙江建业化工股份有限公司 A kind of technique preparing tert-butylamine in raw material dynamic equilibrium
CN112745227A (en) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 Method for preparing tert-butylamine from isobutene and ammonia

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB502737A (en) * 1937-09-23 1939-03-23 Horace Finningley Oxley Improvements in or relating to the production of aliphatic amines
EP0039061A1 (en) * 1980-04-28 1981-11-04 Pennwalt Corporation Preparation of amines from olefins using certain transition metal catalysts
US4314083A (en) * 1980-10-03 1982-02-02 Air Products And Chemicals, Inc. Preparation of linear polyalkylene polyamines
US4459191A (en) * 1981-05-01 1984-07-10 Pennwalt Corporation Light-catalyzed process for preparing amines
US4483747A (en) * 1977-06-21 1984-11-20 Chisso Corporation Monomer removal from the slurry of vinyl chloride resin with steam by using improved plate tower
EP0200923A2 (en) * 1985-04-18 1986-11-12 ATOCHEM NORTH AMERICA, INC. (a Pennsylvania corp.) Preparation of amines from olefins using ammonium halide catalysts

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB502737A (en) * 1937-09-23 1939-03-23 Horace Finningley Oxley Improvements in or relating to the production of aliphatic amines
US4483747A (en) * 1977-06-21 1984-11-20 Chisso Corporation Monomer removal from the slurry of vinyl chloride resin with steam by using improved plate tower
EP0039061A1 (en) * 1980-04-28 1981-11-04 Pennwalt Corporation Preparation of amines from olefins using certain transition metal catalysts
US4314083A (en) * 1980-10-03 1982-02-02 Air Products And Chemicals, Inc. Preparation of linear polyalkylene polyamines
US4459191A (en) * 1981-05-01 1984-07-10 Pennwalt Corporation Light-catalyzed process for preparing amines
EP0200923A2 (en) * 1985-04-18 1986-11-12 ATOCHEM NORTH AMERICA, INC. (a Pennsylvania corp.) Preparation of amines from olefins using ammonium halide catalysts

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108610260A (en) * 2018-06-08 2018-10-02 浙江建业化工股份有限公司 A kind of technique preparing tert-butylamine in raw material dynamic equilibrium
CN108610260B (en) * 2018-06-08 2021-01-08 浙江建业化工股份有限公司 Process for preparing tert-butylamine in dynamic balance of raw materials
CN112745227A (en) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 Method for preparing tert-butylamine from isobutene and ammonia
CN112745227B (en) * 2019-10-31 2023-01-10 中国石油化工股份有限公司 Method for preparing tert-butylamine from isobutene and ammonia

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FR2621313B1 (en) 1990-02-02
ATE72561T1 (en) 1992-02-15
DE310527T1 (en) 1989-08-24
DE3868376D1 (en) 1992-03-26
ES2008066T3 (en) 1993-07-01
EP0310527A2 (en) 1989-04-05
EP0310527A3 (en) 1989-10-04
ES2008066A4 (en) 1989-07-16
GR890300088T1 (en) 1989-10-31
EP0310527B1 (en) 1992-02-12
FR2621313A1 (en) 1989-04-07
GR3004212T3 (en) 1993-03-31

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